JPS63101337A - Production of isobutylene - Google Patents
Production of isobutyleneInfo
- Publication number
- JPS63101337A JPS63101337A JP61245415A JP24541586A JPS63101337A JP S63101337 A JPS63101337 A JP S63101337A JP 61245415 A JP61245415 A JP 61245415A JP 24541586 A JP24541586 A JP 24541586A JP S63101337 A JPS63101337 A JP S63101337A
- Authority
- JP
- Japan
- Prior art keywords
- isobutylene
- acid type
- catalyst
- reaction
- silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010457 zeolite Substances 0.000 claims abstract description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、触媒としてシリカ／アルミナ比が１２以上で
あるゼオライトを用いることを特徴とする第５ブタノー
ル（以下、ＴＢＡと略す）の脱水によるイソブチレンの
製造方法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention is a method of dehydrating 5-butanol (hereinafter abbreviated as TBA), which is characterized by using zeolite having a silica/alumina ratio of 12 or more as a catalyst. The present invention relates to a method for producing isobutylene.
（従来の技術）
従来、ＴＢＡの脱水によるイソブチレンの製造について
は、多くの方法が知られている。アルミナ等の固体酸を
触媒とする公知の方法は、特公昭４８−１０１２１等で
実施されているように１通常、気相で２５０Ｃ以上の高
温で反応を行なうため、インブチ／の異性化反応による
ブチ／−２等が生成し、高純度のイソブチレンを得るこ
とは困難となる。一方＠ ＴＢＡの脱水を比較的低温で
液相で実施する方法も知られている。例えば、硫酸を触
媒とする方法が工業的にも用いられているが、腐食性が
高く、装置が高価になるという問題点がある。この欠点
を回避するために、イオン交換樹脂を用いる方法が、い
くつか提案されている。例えば特開昭５８−１１６４２
７では、イオン交換樹脂を用いた固定床で、８０〜１５
０Ｃの温度範囲でＴＢＡを脱水する方法を開示している
。しかし、この方法で反応理髪が１２０Ｃ以下の場合、
平衡的に不利なため、ワンパスの転化率が低く、ＴＢＡ
および水を多ｔＫＩＪサイクルする必要が生じてしまう
。また、１２０Ｃを超えた温度で反応させようとすると
、ジイソブチレンを生成し、原単位の悪化をきたす。(Prior Art) Conventionally, many methods are known for producing isobutylene by dehydrating TBA. Known methods using a solid acid such as alumina as a catalyst, as carried out in Japanese Patent Publication No. 10121/1987, etc.1, usually carry out the reaction in the gas phase at a high temperature of 250C or higher, so the isomerization reaction of Buty/-2 etc. are produced, making it difficult to obtain high purity isobutylene. On the other hand, a method is also known in which @TBA is dehydrated in a liquid phase at a relatively low temperature. For example, a method using sulfuric acid as a catalyst is used industrially, but it has the problems of being highly corrosive and requiring expensive equipment. In order to avoid this drawback, several methods using ion exchange resins have been proposed. For example, JP-A-58-11642
7, in a fixed bed using ion exchange resin, 80 to 15
A method for dehydrating TBA in a temperature range of 0C is disclosed. However, in this method, if the reaction barber is less than 120C,
Due to equilibrium disadvantage, one-pass conversion rate is low and TBA
Also, it becomes necessary to cycle the water many times through tKIJ. Furthermore, if the reaction is attempted at a temperature exceeding 120C, diisobutylene is produced, resulting in a deterioration of the unit consumption.
（発明が解決しようとする問題点）
上記のように、従来法においては、気相で高温で反応を
行なう方法、比較的低温で液相で実施する方法、また、
イオン又換樹脂を用いる方法いずれにも、それぞれ問題
点があり、これを解決したイソブチレンの製造方法が望
まれていた。(Problems to be Solved by the Invention) As mentioned above, in the conventional methods, there are methods in which the reaction is carried out in the gas phase at a high temperature, methods in which the reaction is carried out in the liquid phase at a relatively low temperature, and
Each method using an ion exchange resin has its own problems, and a method for producing isobutylene that solves these problems has been desired.
（問題点を解決するための手段）
本発明者らは、イソブチレンを製造する際の前記の問題
点を解決するため鋭意検討を進めた結果、触媒としてシ
リカ／アルミナ比が１２以上の酸型ゼオライトを用いる
ことにより、高選択率かつ高転化率でイソブチレンを得
ることができることを見出し、本発明に到達した。(Means for Solving the Problems) As a result of intensive studies to solve the above-mentioned problems when producing isobutylene, the present inventors found that an acid type zeolite with a silica/alumina ratio of 12 or more was used as a catalyst. It was discovered that isobutylene can be obtained with high selectivity and high conversion rate by using this method, and the present invention was achieved based on this discovery.
本発明において用いるゼオライトは、シリカ／アルミナ
の比率が１２以上の酸型ゼオライトであシ、代表的には
Ｈ−ＺＳＭ−５等が用いられる。The zeolite used in the present invention is an acid type zeolite having a silica/alumina ratio of 12 or more, and H-ZSM-5 or the like is typically used.
シリカ／アルミナ比の低いゼオライトを用いた場合には
、活性が低くなり実用的ではない。If a zeolite with a low silica/alumina ratio is used, the activity will be low and it is not practical.
反応温度は、およそ９０〜１７０Ｃの範囲で実施される
が、本発明を特に有利に行なうには。The reaction temperature is carried out in the range of approximately 90-170C, which is particularly advantageous for carrying out the invention.
１２０〜１６０Ｃの温度が好ましく、高転化率かつ高選
択率の反応が可能となる。A temperature of 120 to 160C is preferable, allowing a reaction with high conversion and high selectivity.
本発明において１反応圧力は特に規定されることなく、
なりゆきでよいが、生成するイソブチレンガスが、５気
圧以上の条件にすることは、工業用常用の冷却剤で凝縮
できるという点で有利である。In the present invention, 1 reaction pressure is not particularly defined,
Although anything is possible, it is advantageous that the isobutylene gas produced is under conditions of 5 atm or higher in that it can be condensed with a common industrial refrigerant.
本発明のＴＢＡ原料は、必ずしも純粋でなくてもよく、
反応φ件下で化学反応をおこさない有機物が少量混入し
たものも用いることができる。また、水分を含むＴＢＡ
を用いることも可能である。The TBA raw material of the present invention does not necessarily have to be pure,
It is also possible to use a mixture containing a small amount of organic substance that does not cause a chemical reaction under the reaction conditions. In addition, TBA containing water
It is also possible to use
本反応は、固定床あるいは攪拌槽等、工業用常用の装置
で実施することができる。This reaction can be carried out in a commonly used industrial apparatus such as a fixed bed or a stirred tank.
（実施例）
以下に実施例を上げて具体的に説明するが、本発明は、
これに限定されるものではない。(Example) The present invention will be specifically explained below with reference to Examples.
It is not limited to this.
実施例１
内径１０ｍｍ、長さ６０ｆｆ１１ｍのＳＵＳパイプに焼
結フィルターをセットした反応管に、シリカ／アルミナ
比が４０（７）Ｈ−ＺＳＭ−ｓノパウター１．６１を充
填した後、ＴＢＡの８２％水溶液を１０ＤＣに予熱して
８０９／Ｈｒ でフィードし、所定温度所定圧力で反応
させた。反応生成物をガスクロマトグラフィーで分析し
、反応成績を求めた。結果を表１に示す。Example 1 A reaction tube in which a sintered filter was set in a SUS pipe with an inner diameter of 10 mm and a length of 60 ff and 11 m was filled with silica/alumina ratio of 40 (7) H-ZSM-s powder 1.61, and then 82% of TBA The aqueous solution was preheated to 10 DC and fed at 809/Hr, and reacted at a predetermined temperature and a predetermined pressure. The reaction products were analyzed by gas chromatography to determine the reaction results. The results are shown in Table 1.
実施例２
触媒としてシリカ／アルミナ比が１５０のＨ−ＺＳＭ−
５を用いた以外は、実施例１と同様の方法で反応を行な
った。結果を表１に示す。Example 2 H-ZSM- with a silica/alumina ratio of 150 as a catalyst
The reaction was carried out in the same manner as in Example 1, except that 5 was used. The results are shown in Table 1.
比較例１へ２
陽イオン又換樹脂（ローム・アンド・ハース社製、アン
バーライト＋ｚＯＢｌを常用の方法で酸処理した触媒を
用いた他は、実施例１と同様な方法で反応を行なった（
比較例１）。Comparative Example 1 to 2 A reaction was carried out in the same manner as in Example 1, except that a catalyst obtained by acid-treating cation conversion resin (manufactured by Rohm & Haas, Amberlite + zOBl in a conventional manner) was used (
Comparative example 1).
同様に、シリカ／アルミナ比が１０の酸型ゼオライトで
あるガスクロ工業社製Ｚｅｏｌｏｎ ９００ Ｈを用い
た場合の結果を表１に示す。Similarly, Table 1 shows the results when Zeolon 900 H manufactured by Gascro Kogyo Co., Ltd., which is an acid type zeolite with a silica/alumina ratio of 10, was used.
表 １
（発明の効果）
上記実施例から判るように１本発明によれば、第３ブタ
ノールの脱水によりイソブチレンを製造する方法におい
て、高選択率かつ高転化率でイソブチレンを得ることが
できる。Table 1 (Effects of the Invention) As can be seen from the above examples, according to the present invention, isobutylene can be obtained with high selectivity and high conversion rate in the method of producing isobutylene by dehydration of tertiary butanol.
Claims (3)
する方法において、触媒としてシリカ／アルミナ比が１
２以上である酸型ゼオライトを用いることを特徴とする
イソブチレンの製造方法。(1) In a method for producing isobutylene by dehydration of tertiary butanol, a silica/alumina ratio of 1 is used as a catalyst.
1. A method for producing isobutylene, characterized in that an acid type zeolite having an acid type of 2 or more is used.
行なう特許請求の範囲第１項記載の方法。(2) The method according to claim 1, wherein the dehydration reaction of tertiary butanol is carried out at 120 to 160°C.
範囲第１項記載の方法。(3) The method according to claim 1, in which acid type ZSM-5 is used as the catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61245415A JPS63101337A (en) | 1986-10-17 | 1986-10-17 | Production of isobutylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61245415A JPS63101337A (en) | 1986-10-17 | 1986-10-17 | Production of isobutylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63101337A true JPS63101337A (en) | 1988-05-06 |
Family
ID=17133313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61245415A Pending JPS63101337A (en) | 1986-10-17 | 1986-10-17 | Production of isobutylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63101337A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6518474B1 (en) | 1999-10-29 | 2003-02-11 | Huntsman International Llc | Process for producing isobutylene from tertiary butyl alcohol |
-
1986
- 1986-10-17 JP JP61245415A patent/JPS63101337A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6518474B1 (en) | 1999-10-29 | 2003-02-11 | Huntsman International Llc | Process for producing isobutylene from tertiary butyl alcohol |
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